Calcium chloride and method of making same



April 5, 1932. s HEATH 1,852,303

CALCIUM CHLORIDE ANDVMETHOD OF MAKING SAME Filed Nov 6, 1928 HQ! f/ak (approx. 77% (h6/L) ai fem/: a/bprox. 160 C Cooec, surface crz'ec/ pracucif (a/bray, 78 79% Caf/z) at Temp. al1/:rox 80C.

IN VEN TOR,

ATTORNEY lpatcnted Apr. t, i932 UNITED STATES rasant PATENT OFFICE BHELDON .'B. HEATH, OF MIDLAND; MICHIGAN, ASSIGNOR T0 THE DOW CHEMICAL COMPANY, OF MIDLAND, MICHIGAN, A CORPORATION OF MICHIGAN cancion cnLomDE AND Mannen or mme am 'Application led November 6, '1928. Serial No. 317,507.

My invention relates to improvements in the preparation of calcium chloride containing water of crystallization in the form of particles exhibiting free-Howling characteristics and reduced tendency to cake in the package.

Calcium chloride is produced in large quantity, particularly in the form of particles which are free-flowing and exhibit nony@ calring tendency in the package. These particles contain preferably less crystal water than corresponds to the dihydrate CaCl22H2O. 'lhe so prepared particles are then supercially dried by bringing them into counter i current relation with a heated current of air, specifically the products of combustion of fuel. They are then cooled in a counter current of air to condition them for packaging. ln the prevailing method, a solution of i to calcium chloride is concentrated by boiling to a composition ranging from 71 to 5 per cent. anhydrous calcium chloride and is then Haired. I have noted that if sufliciently` hot particles of such Haired calcium chloride be at subjected to cooling in a counter current of air, they become superlicially dried, losing from one and one-half to two per cent. of moisture which is self evaporated by the heat content ot the particles without the aid of enternal heat from fuel or otherwise.

llo the accomplishment of the foregoing result, the invention, then, consists of the y,steps and product hereinafter fully described and particularly pointed out in the claims, the annexed drawing illustrating one typical torni of apparatus adapted for the carrying out of such steps, such disclosed apparatus constituting, however, but one of the various ways in which the principle of the invention may be used.

ln said annexed drawing The single figure there appearing illustrates in diagrammatic fashion an apparatus arranged for the carrying out of my` improved process or method.

Une mode of practicing my improved method accordingly comprises cooling a-hot divided forni of calcium chloride containing water of crystallization in a current of air, preferably' in counter current relation,

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whereby water-is removed from the surface layers of the so treated particles, and I obtain thereby a product exhibiting free-flowing and non-caking characteristics vwithout employing outside heat for the superficial drying.

I have found it possible to produce a granular or iiaked form of calcium chloride containing markedly less water ofvcrystalliza.- tionthan-corresponds to the dihydrate c stal by solidifying in the aforesaid subdivi ed form a slurry comprised of crystals of the mono-hydrate in a mother liquid saturated with same at the atmospheric Vboiling point thereof, such method being more particularly described and claimed in my copending application y Serial No. 343,961, filed March 2, 1929. I have now discovered further that if hot particles of calcium chloride thus made from such a slurry are at once subjected to air cooling in counter current as described, a satisfactory packaging grade of chloride will be so obtained without the use of furnace heat for supercial drying. Such procedure accordingly constitutes another mode of nracticingmy improved method.

More specifically, I have discovered that if the calcium chloride solution be concentrated to salt out the monohydrate crystals producing a thick slurry which may still be caused to How, as by pumping, and having a nishing temperature of approximately 178 C.,

(or more, if concentrated under pressure),

such a slurry has a very sharp freezing point forming upon iaking a good hardstrong particle above 160 C., such particles then containing enough heat to eifect self evapo- Sli ration of one and one-half to two per cent.

of water when cooled in a counter current l air cooler. For example, if the hot particles at 160 C. contain 77 per cent. CaClz, the cooled product at 80 C. will analyze from 78 to 79 per cent. CaClg. the increase in percentage content of anhydrous solids4 being due to removal of water from the surface layers of the so treated particles.

I may further concentrate the solution of calcium chloride under pressure in excess of atmospheric pressure, finishing at a still higher temperature and then proceed to solidify ioo and form into particles the solidiedsalt, followingwith cooling of the so formed still hot particles as described. Such procedure constitutes still another mode of practiclng my im roved method.

referred method of ornnng the particles 1s to flake the mixture of crystals and mother liquor upon a rotary tlakmg drum, either di ping into the mixture of crystals and mot er llquor, or havin the mixture fed onto the drum and distri uted thereon by suitable means.

In thev accompanying dra-wing the smgle iigure there appearin indicates in more or less diagrammatic form of procedure. The calcium chlorlde solution is concentrated by boiling in the kettle 1 provided with an agitator, and steam coils to supply the heat. When concentrated to a consistency, due tosalting out of monohydrate cr stals, as thick as may be handled convenient y, the slurry is then run or pumped to the flaker drum 2 upon which it forms a thin sheetof solidified chloride, 'being delivered by the knife 3 to the conveyor 4 as a hot liaked roduct. The hot flaked product is then fe to the rotary cooler 5 from which it emer es to the conveyor 6 in the cooled supericialydried condition. An exhauster 7 draws a current of'air through the cooler. The latter may be' advantageously provided with a series of shovels 8 for lifting the iakes and dropping them through the air current.

Other methods of producing particles may be employed, such as spraying the hot slurry with an air or steam jet into a collecting chamber and then cooling same in the manner described or the slurry may be allowed to cool and solidify in suitable molds, .such as shallow pans, and then afterwards be broken up and granulated and fed to the cooler for superficial drying while still sulliciently hot v for the purpose.

By means of my improvedmethod I am able to obtain, without employing the customary step of drying by furnace heat, a laked or granulated productphaving freeowing and non-caking characteristics.

Other forms may be employed embod g the features -of m invention instead o the one here explaine change being made in the form or construction,.provided the elements stated by any of the following claims or the e uivalent of such stated elements be emp oyed, whether produced by my preferred method or by others embodying steps equivalent to those stated in the following claims.

I therefore particularly point out and distinctly claim as my inventlon 1. In a method o reparing 'a vpartially dehydrated calcium c loride 1n the form of supericially dried particles, the ste s which consist in chilling and mechanica comminutin a mixture of calcium c oride monohy rate crystals and the mother liquor ashion the preferred.

asbases thereof to solidify the same in the form of solid articles and air-cooling the particles, where y the latter are superficial y drated by self-evaporation of water.

2. In a method of preparing a partiall dehydrated calcium chloride in the form o dehyv supericially dried particles, the steps which consist in flaking a mixture of calcium chloride monohydrate crystals and the mother liquor thereof and air-cooling'the flake particles, whereby the latter are supericially dehydrated by self-evaporation of water.

3. In amethod of reparing a partially des hydrated calcium clhloride in the form of superflcially dried particles, the ste s which consist in chill'ng and mechanica ly comminuting a mixture of calciumv chloride monoh rate crystals and the mother liquor thereo to solidlfy the same in the form of solid particles and contactin theparticles while still hot with a counterowing current of unheated air, whereb the latter are cooled and supericially dehy ated by self-evaporation of water.

4. In a method of preparing a partially dehydrated calcium chloride in the form of superciall dried particles, the steps which consistir! t king a mixture of calcium chloride monoh drate crystals and the mother liquor thereo and contacting the Hake part1- cles while still hot with a counter-flowing current of unheated air, whereby the latter are cooled and supericially dehydrated by selfevaporation of water.

5. The method of reparing a partially dehydrated calcium c loride 1n the form of supercially dried particles which comprises concentrating a solution of calicum chloride Y by evaporation until the CaClz content thereofis in excess of 75 per cent, chilling and mechanically comminutin the hot concentrated mixture of crystals an mother liquor thereby obtained to solidi the same in the form of solid particles an contacting the particles while still hot with a counter-flowing current of unheated air, whereby the latter are cooled and superclally dehydrated by self-evaporation o water.

6. The method of preparing a partially dehydrated calcium chloride in the form of supericially dried particles which comprises concentrating a solution of calcium chloride by eva eration-to salt out cr stals of'calcium chlori e monohydrate and orm a slurry of crystals and mother liquor thereof having a consistency to permit pumping, chilling and mechanically comminuting the slurry to solidify the same in the form of solid particles and contacting the particles whilev still hot with a counter-flowing current of unheated air, whereby the latter are cooled and supericially dehydrated by self-evaporation of water.

7. The method of reparing a partially dehydrated calcium c loride )1n the form of supericially dried particles which com rises concentrating a solution of calcium c oride by evaporation to a temperature of approximately 178 C., chillin and mechanically comminuting a mixture cgi crystals and mother liquor thereby obtained to solidfy the same in the form of solid particles and contacting the particles While still hot with a counterilowing current of unheated air wherel7 the latter are cooled and superficially ehydrated by self-evaporation of Water.

8. The method of preparing a partially dehydrated calcium chloride in the form of superficially dried particles which comprises concentrating a solution of calcium chloride by evaporation to a temperature of approximately 178 C., ila-king the crystal slurry thereby obtained to solidify the same in the form of solid particles and contacting the particles While still hot with a counter-flowing current of unheated air, whereb the latter are cooled and supercially dehydrated by self-evaporation of water.

Signed by me Athis 17th.day of October,

SHELDON B. HEATH. 

